CN105914388A - Lead methanesulfonate flow battery electrolyte - Google Patents

Lead methanesulfonate flow battery electrolyte Download PDF

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Publication number
CN105914388A
CN105914388A CN201610246329.5A CN201610246329A CN105914388A CN 105914388 A CN105914388 A CN 105914388A CN 201610246329 A CN201610246329 A CN 201610246329A CN 105914388 A CN105914388 A CN 105914388A
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China
Prior art keywords
electrolyte
battery
plate
positive
acid lead
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CN201610246329.5A
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Inventor
刘政
李远发
赵健
蒋百铃
侯靖媛
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Hao Fa Environmental Protection Science And Technology (shenzhen) Co Ltd
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Hao Fa Environmental Protection Science And Technology (shenzhen) Co Ltd
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Priority to CN201610246329.5A priority Critical patent/CN105914388A/en
Publication of CN105914388A publication Critical patent/CN105914388A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/18Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184Regeneration by electrochemical means
    • H01M8/188Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00Electrolytes
    • H01M2300/0002Aqueous electrolytes
    • H01M2300/0005Acid electrolytes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an application of NaF as an additive in a lead methanesulfonate flow battery electrolyte. The electrolyte is a mixture liquid of lead methanesulfonate and methanesulfonic acid, wherein the concentration of the (CH3SO3)2Pb is 0.1-2 M, the concentration of the CH3SO3H is 0-1 M and the concentration of the NaF is 0.005-0.02 M. The NaF, as the additive, prolongs the service life and improves Coulomb efficiency of a battery, wherein the service life of the battery can reach more than 1000 times, the Coulomb efficiency is basically more than 90%, and energy efficiency is higher than 78%.

Description

A kind of pyrovinic acid lead fluid cell electrolyte
Technical field
The present invention relates to flow battery field, a kind of can improve making of pyrovinic acid lead flow battery With life-span and the electrolysis additive of coulombic efficiency, and this additive is in pyrovinic acid lead flow battery Application.
Background technology
The fast development of global economy so that the demand for the energy constantly increases and primary energy is supplied not Foot, so developing other regenerative resources (wind energy, solar energy etc.) to become focus of concern.But These regenerative resources face fluctuation, intermittence and the uncertain factor such as dispersiveness, randomness and restrict its Development, so that high-efficiency energy-storage technology solves renewable energy power generation Unsteady characteristics.With other energy storage skill Art is compared, and flow battery is more suitable for regenerative resource electric energy electric power storage and conversion.It has many excellent features: Capacitance of storage is big, energy efficiency is high, activation polarization is little, can deep discharge, can realize fast charging and discharging, The advantages such as the feature of environmental protection is good, it is adaptable to extensive electric power storage.This pyrovinic acid lead flow battery used by invention belongs to In one full appositional pattern single flow battery.
Pyrovinic acid lead flow battery is with acidic methylene sulfonic acid lead as electrolyte, and both positive and negative polarity all uses conduction poly- Compound based composites.Electrolyte and battery are independently placed, and electrolyte is transferred to inside battery by pump.? Pb solvable during charging2+Aoxidize on positive and negative electrode respectively, reduction reaction generates PbO2With Pb sinking Amassing at electrode surface, during electric discharge, positive and negative deposit aoxidizes, reduction reaction generates Pb2+It is dissolved in electrolysis In liquid.When discharge and recharge, on positive and negative electrode, there are electric field, velocity field, temperature and concentration etc. common in battery Effect.
The concrete reaction principle of pyrovinic acid lead flow battery is as follows:
Positive pole: Pb2++2H2O-2e→PbO2+4H+, E0=1.455V;
Negative pole: Pb2++ 2e → Pb, E0=-0.126V;
Overall reaction: 2Pb2++2H2O→Pb+PbO2+4H+
Pyrovinic acid lead flow battery does not uses the expensive material such as amberplex because having, and structure simplifies, ratio The particular advantages such as energy is high and there is the biggest development prospect.But pyrovinic acid lead flow battery there is also one A little not enough: service life cycle is short, positive pole electrodeposit brown lead oxide is easy to fall off, energy efficiency and reserve of electricity It is also required to improve further etc. performance.By substantial amounts of experiment and literature research, at pyrovinic acid lead liquid flow electricity The method adding additive NaF in the electrolyte in pond can not only improve battery performance, and economical, effectively. Additive NaF can extend the discharge and recharge life-span of battery and improve the coulombic efficiency of battery.
Sodium fluoride is white powder, is dissolved in water, and the aqueous solution is alkalescent, low price, is a kind of good Electrolysis additive.Additive NaF is incorporated into electrolyte and the impact of battery performance is mainly being improved battery just Pole deposit PbO2Electro catalytic activity and stability.Battery is F when charging-Ion can enter into positive pole and sink Long-pending thing PbO2Intracell.Replace a part of oxygen atom, form F-PbO2Complex, occupies free oxygen atom The passage of diffusion, therefore inhibits at electrode interface nascent state free oxygen atom to PbO2Bulk diffusion.One side Face, maintains PbO2The stoichiometric number of middle oxygen is less than 2, maintains oxygen vacancies concentration, is conducive to maintaining electricity The stability of pole.On the other hand, effectively avoid deterioration and basic unit's oxidation of coating character, and suppress PbO2Anodic solution, extend PbO2Anode life.Therefore electrolysis additive NaF can improve The coulombic efficiency of pyrovinic acid lead flow battery and service life.
Summary of the invention
It is an object of the invention to overcome pyrovinic acid lead flow battery to presently, there are short the lacking of service life cycle Point, improves the performance of battery in terms of electrolysis additive, adds and add in pyrovinic acid lead electrolytic solution Add anode reactant PbO when agent NaF can improve battery charging2Electro catalytic activity and stability, thus carry Coulombic efficiency that high battery is overall and discharge and recharge life-span.NaF additive improves life-span and the coulomb of battery Efficiency, wherein the life-span of battery can reach more than 1000 times, coulombic efficiency substantially more than 90%, energy Efficiency is more than 78%.
Pyrovinic acid lead fluid cell electrolyte, for assembling in the battery of use, described assembles the battery used Including with lower part:
Base plate: base plate uses aluminum alloy plate materials, is used for fastening pile, prevents electrolyte from revealing, size For: 12.5cm × 10.5cm.
Positive and negative pole plate: positive/negative plate uses PVC material, size is: 12cm × 10cm, positive and negative Milling out size in the middle of pole plate is: 2cm × 5.8cm, and thickness is the groove of 4mm, is used for embedding conducting polymer base multiple Condensation material electrode.
Runner: the exterior contour of runner is identical with the area of positive and negative pole plate, the area of inner flow passage and conduction The effective area of plate is identical.
Positive and negative electrode conductive plate: the conducting polymer based composites that positive and negative electrode conductive plate all uses, will lead Electric polymer base composite board and copper mesh be tailored into 2cm × 5.8cm size together with wire at 200-250 DEG C and 5-10kgf/cm2Hot-forming and cool to the furnace take out after normal temperature.Conductive plate after hot pressing is repaired further Become original size 2cm × 5.8cm.
Battery assembles: by positive and negative conductive plate silica gel sealing to the groove of positive and negative pole plate, to prevent electricity Solve the leakage of liquid.Order screw rod group according to aluminum alloy bottom plate-positive plate-runner-negative plate-aluminum alloy bottom plate Dress.
According to an aspect of the present invention, the invention provides a kind of pyrovinic acid lead fluid cell electrolyte, Described pyrovinic acid lead fluid cell electrolyte is by (CH3SO3)2Pb、CH3SO3H, purified water and additive NaF Composition, wherein (CH3SO3)2The concentration of Pb is 0.1-2M, CH3SO3The concentration of H is the dense of 0-1M, NaF Degree is 0.005-0.02M.
Preferably, (CH3SO3)2The concentration of Pb is 1.5-1.8M, CH3SO3The concentration of H is 0.3-0.9M, The concentration of NaF is 0.01-0.015M.
According to another aspect of the present invention, the invention provides a kind of pyrovinic acid lead fluid cell electrolyte Preparation method, first deionized water is slowly added into CH3SO3H dilutes, then at PbCO3Add A small amount of deionized water, by the CH after dilution3SO3H is slowly added to PbCO3In the aqueous solution and ceaselessly Stirring, until reaction is completely, adds deionized water and dilutes to obtain the most additivated electrolyte;
In the most additivated electrolyte, add NaF additive again, after stirring, obtain pyrovinic acid lead Fluid cell electrolyte.
Charge-discharge procedures is arranged: charging and discharging currents density is 10-40mA/cm2, charging interval 0.5-2h, electrolysis Liquid line flow velocity in the battery is 0.5-5cm/s.
Compared with prior art, due to the fact that employing NaF as electrolysis additive, containing this interpolation The pyrovinic acid lead flow battery of agent improves anode deposit PbO2Electro catalytic activity and stability, and And extend the anode life of brown lead oxide.Thus additive NaF improve battery coulombic efficiency and make Use the life-span.Special is 10mA/cm in the density of charging current2, the battery when amount of additive NaF is 0.01M The coulombic efficiency of discharge and recharge substantially more than 90%, energy efficiency is more than 78%, and battery life reaches 1000 Secondary.
Accompanying drawing explanation
Fig. 1 is the coulombic efficiency of A battery and the figure of cycle-index in example 1;
Fig. 2 is the energy efficiency of A battery and the figure of cycle-index in example 1;
Fig. 3 is the coulombic efficiency of B battery and the figure of cycle-index in example 1;
Fig. 4 is the energy efficiency of B battery and the figure of cycle-index in example 1;
Fig. 5 is the coulombic efficiency of C battery and the figure of cycle-index in example 2;
Fig. 6 is the energy efficiency of C battery and the figure of cycle-index in example 2;
Fig. 7 is the coulombic efficiency of D battery and the figure of cycle-index in example 2;
Fig. 8 is the energy efficiency of D battery and the figure of cycle-index in example 2.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention of greater clarity, below in conjunction with specific embodiment party Formula, the present invention is described in more detail.It should be understood that these describe the most exemplary, and do not really want Limit the scope of the present invention.
Embodiment 1
The electrolyte of preparation pyrovinic acid lead flow battery in fume hood:
1) deionized water is slowly added into CH3SO3H dilutes, then at PbCO3Add go on a small quantity from Sub-water, by the CH after dilution3SO3H is slowly added to PbCO3In the aqueous solution and be continuously agitated, directly To reaction completely, add deionized water and dilute to obtain the most additivated electrolyte;Wherein (CH3SO3)2Pb is 1.8mol:CH3SO3H is 0.3mol, altogether 1L.
2) the most averagely pour in the electrolyte bottle of two 500ml.
A electrolyte: add the NaF of 0.005mol in the 500ml electrolyte just now prepared, uniform stirring, Electrolyte as pyrovinic acid lead flow battery.
B electrolyte: without any additive.
Pyrovinic acid lead flow battery assembles in the manner described above, carries out even with A, B electrolyte and pump pipe Connect, fully put test.The parameter of charge-discharge test is arranged: charging and discharging currents density is 10mA/cm2, Charging interval 2h, electrolyte line flow velocity in the battery is 0.5-5cm/s.Result display A electrolyte adds The battery coulombic efficiency of 0.005mol NaF is more than 90%, and energy efficiency is 78-85%, the charge and discharge cycles longevity Life is 1000 times.The coulombic efficiency of B battery is 70-90%, and energy efficiency is 60-80%.
Embodiment 2
The electrolyte of pyrovinic acid lead flow battery is prepared: method is with embodiment 1, wherein in fume hood (CH3SO3)2Pb:CH3SO3H=1.5:0.9 (M), altogether 1L.
Pour into respectively in the electrolyte bottle of two 500ml.
C electrolyte: add the NaF of 0.0075mol, uniform stirring in the electrolyte just now prepared, use Make the electrolyte of pyrovinic acid lead flow battery.
D electrolyte: without any additive.
Pyrovinic acid lead flow battery assembles in the manner described above, carries out even with C, D electrolyte and pump pipe Connect, fully put test.The parameter of charge-discharge test is arranged: charging and discharging currents density is 10mA/cm2, Charging interval 2h, electrolyte line flow velocity in the battery is 0.5-5cm/s.The coulomb effect of result display C battery Rate is 90-91%, and energy efficiency is 74-77%.The coulombic efficiency of D battery is 70-90%, and energy efficiency is 50-80%.

Claims (4)

1. a pyrovinic acid lead fluid cell electrolyte, described pyrovinic acid lead flow battery is electrolysed Liquid is by (CH3SO3)2Pb、CH3SO3H, purified water and additive NaF composition, wherein (CH3SO3)2Pb Concentration be 0.1-2M, CH3SO3The concentration of H be the concentration of 0-1M, NaF be 0.005-0.02M.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that: (CH3SO3)2The concentration of Pb is 1.5-1.8M, CH3SO3The concentration of H is the dense of 0.3-0.9M, NaF Degree is 0.01-0.015M.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that: Its preparation method comprises the following steps:
1) battery electrolyte according to claim 1 composition, first by deionized water lentamente Join CH3SO3H dilutes, then at PbCO3Add a small amount of deionized water, after dilution CH3SO3H is slowly added to PbCO3In the aqueous solution and be continuously agitated, until reaction is completely, Add deionized water and dilute to obtain the most additivated electrolyte;
2) in the most additivated electrolyte, add NaF additive, after stirring, obtain methyl Sulfonic acid lead fluid cell electrolyte.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that: Pyrovinic acid lead fluid cell electrolyte, for assembling in the battery of use, described assembles the battery used Including with lower part:
Base plate: base plate uses aluminum alloy plate materials, is used for fastening pile, prevents electrolyte from revealing, A size of: 12.5cm × 10.5cm;
Positive and negative pole plate: positive/negative plate uses PVC material, a size of: 12cm × 10cm, Milling out a size of in the middle of positive/negative plate: 2cm × 5.8cm, thickness is the groove of 4mm, is used for embedding conduction Polymer matrix composite electrode;
Runner: the exterior contour of runner is identical with the area of positive and negative pole plate, the area of inner flow passage with The effective area of conductive plate is identical;
Positive and negative electrode conductive plate: the conducting polymer based composites that positive and negative electrode conductive plate all uses, Conducting polymer base composite board and copper mesh are tailored into 2cm × 5.8cm size together with wire 200-250 DEG C and 5-10kgf/cm2Hot-forming and cool to the furnace take out, after hot pressing after normal temperature Conductive plate is trimmed to original size 2cm × 5.8cm further;
Battery assembles: by positive and negative conductive plate silica gel sealing to the groove of positive and negative pole plate, in case The only leakage of electrolyte, according to the order of aluminum alloy bottom plate-positive plate-runner-negative plate-aluminum alloy bottom plate Assemble with screw rod.
CN201610246329.5A 2016-04-20 2016-04-20 Lead methanesulfonate flow battery electrolyte Pending CN105914388A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711486A (en) * 2016-12-13 2017-05-24 华中科技大学 Lead redox flow battery electrolyte
CN108832164A (en) * 2018-05-28 2018-11-16 华中科技大学 A kind of lead fluid cell electrolyte containing compound additive
CN109873191A (en) * 2019-03-29 2019-06-11 西安理工大学 A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery
CN110190312A (en) * 2019-06-25 2019-08-30 西安理工大学 A kind of lead flow battery electrolyte
CN112838255A (en) * 2021-01-28 2021-05-25 西安理工大学 Efficient stable electrolyte of lead single flow battery and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US4400449A (en) * 1980-01-10 1983-08-23 Peter O. Henk Lead salt electric storage battery
CN101567459A (en) * 2008-04-25 2009-10-28 北京化工大学 Acid single flow cell
CN101853956A (en) * 2010-06-12 2010-10-06 江苏华富控股集团有限公司 Lead-acid flow battery
CN102723519A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 Lead liquid flow battery electrolyte
CN102723518A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 All-lead liquid flow battery
US20150180088A1 (en) * 2012-07-20 2015-06-25 Commissariat A L'energie Atomique Et Aux Energies Alternatives Electrochemical lead battery including a specific additive

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400449A (en) * 1980-01-10 1983-08-23 Peter O. Henk Lead salt electric storage battery
CN101567459A (en) * 2008-04-25 2009-10-28 北京化工大学 Acid single flow cell
CN101853956A (en) * 2010-06-12 2010-10-06 江苏华富控股集团有限公司 Lead-acid flow battery
CN102723519A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 Lead liquid flow battery electrolyte
CN102723518A (en) * 2011-03-30 2012-10-10 中国人民解放军63971部队 All-lead liquid flow battery
US20150180088A1 (en) * 2012-07-20 2015-06-25 Commissariat A L'energie Atomique Et Aux Energies Alternatives Electrochemical lead battery including a specific additive

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711486A (en) * 2016-12-13 2017-05-24 华中科技大学 Lead redox flow battery electrolyte
CN106711486B (en) * 2016-12-13 2020-05-19 华中科技大学 Lead flow battery electrolyte
CN108832164A (en) * 2018-05-28 2018-11-16 华中科技大学 A kind of lead fluid cell electrolyte containing compound additive
CN109873191A (en) * 2019-03-29 2019-06-11 西安理工大学 A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery
CN109873191B (en) * 2019-03-29 2021-06-15 西安理工大学 Lead flow battery seasonal-resistant electrolyte and preparation method thereof
CN110190312A (en) * 2019-06-25 2019-08-30 西安理工大学 A kind of lead flow battery electrolyte
CN110190312B (en) * 2019-06-25 2021-01-15 西安理工大学 Electrolyte for lead flow battery
CN112838255A (en) * 2021-01-28 2021-05-25 西安理工大学 Efficient stable electrolyte of lead single flow battery and preparation method thereof

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